CN85109199A - 一种用于窗玻璃，特别是受大气影响的窗玻璃的具有自复性能的涂层 - Google Patents

一种用于窗玻璃，特别是受大气影响的窗玻璃的具有自复性能的涂层 Download PDF

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CN85109199A
CN85109199A CN85109199.7A CN85109199A CN85109199A CN 85109199 A CN85109199 A CN 85109199A CN 85109199 A CN85109199 A CN 85109199A CN 85109199 A CN85109199 A CN 85109199A
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英格里德·穆西尔
格哈特·霍尔萨
赫尔默·雷迪施
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Abstract

本发明涉及一种用于窗玻璃和/或塑料，特别是暴露在大气作用下的，具有自复性能的聚氨酯涂层。
根据本发明的涂层是由三官能团的异氰酸酯成分，例如含有15～25％(重量)NCO基团的1，6-己二异氰酸酯的缩二脲或异氰酸酯和一种选自含有约3～12％(重量)OH基团的多官能团的聚酯多元醇的多元醇成分所组成的反应混合物所制成的。

Description

本发明涉及一种用于窗玻璃和/或塑料的具有自复性能的聚氨酯涂层，这种涂层是由一种含多官能团的异氰酸酯成分，特别是一种三官能团的异氰酸酯成分和多官能团的多元醇成分的反应混合物，以及选用的反应催化剂和其他辅助物质所制成。
具有自复性能的聚氨酯涂层特别是可用作硅酸盐窗玻璃的防碎层，例如，用于机动车上的挡风玻璃。举例来说，在法国专利说明书2187719和2251608中也描述了这种用途。安置在车内面向着旅客车厢的窗玻璃上的这种涂层，在发生玻璃窗碎裂时，可以防止玻璃碎片的锐边与车厢内的物体直接接触。在这样的安装中，涂层由玻璃层保护而不直接受大气的影响。
上述类型的涂层也可用作透明塑料的涂层。德国专利说明书2058504、2634816和3201849都描述了这样一种用途。在这种情况下，聚氨酯层用于改良塑料的耐擦伤性能。上面所说到的聚氨酯层实际上是具有自复性能的，就是说，在这种层表面上的损伤在短时间内会自然消失，而这种消失所需时间一般是温度的函数。这种自复聚氨酯涂层也可以用于暴露在大气中的玻璃和/或塑料外表面的涂层，或者改善塑料的耐擦伤性，或者改善玻璃的耐磨损性。事实上，已经知道，这种软的涂层也基本上十分适宜于改善玻璃的耐磨损性，例如，用于暴露在飞沙环境中的玻璃上。
已知的聚氨酯涂层不仅具有耐擦伤性和其它耐磨性的有用性能，而且也具有长期保持这些性质的有用性能，但只能在涂层不同时暴露在光、热和温度的作用下，也就是说，不暴露在大气中，即没有受到太阳直接辐照，同时也没有湿气和雨的条件下才具有这些有用性能。人们发现，将这种涂层暴露在坏天气条件中时，经过一段时间的光和水解浸蚀的联合作用，涂层表面就受到浸蚀。经过一定时期后，用肉眼就能观察到表面上的这种剥蚀状况，并且这种剥蚀状况持续不断地进行。因此，这些已知组合物的涂层不宜长期用于窗玻璃的外表面上，也就是说，不宜用于直接暴露在外面大气中的窗玻璃的外表面上。
本发明提出了一种上述类型的新的聚氨酯透明自复涂层，该涂层除了具有所需的，特别是耐擦伤和耐磨损性能的优良物理和化学性质以外，还具有抗恶劣天气作用的改进性能，特别是能同时抗光和温度作用的改进性能。
本发明涂层是由以含有15%到25%（重量）NCO基团的1，6-己二异氰酸酯单体，如缩二脲或异氰脲酯为基的，主要是三官能团的脂族聚合物作为异氰酸酯成分，和以含有3～12%（重量）OH基团的多功能聚酯多元醇作为多元醇成分的反应混合物所制成的。
利用明确化学组分的异氰酸酯成分和多元醇成分，制得化学结构也确定的聚氨酯涂层，该涂层除了具有耐擦伤、实用和耐磨的必要物理-化学性质以外，还具有所希望的抗恶劣天气的性能。因此这些涂层适用于直接暴露在坏天气中的外表面上。
作为异氰酸酯成分，可以使用由含有约20～23%（重量）NCO基团的1，6-己二异氰酸酯所得的主要为三官能团的聚异氰脲酯。作为变更，也可以使用由含有21～25%NCO游离基团的1，6-己二异氰酸酯所得的主要为三官能团的缩二脲。
在本发明的一个优良方案中，作为多元醇成分，可以使用以含有3～5%（重量）OH基团的三羟甲基丙烷、1，6-己二醇、己二酸和邻-及异-苯二甲酸为基的，轻度支链的聚酯多元醇。
在另一个优良方案中，将以三羟甲基丙烷或丙三醇和含有相当于约8～12%（重量）OH基团的己酸内脂为基的三官能团内脂聚酯多元醇用作多元醇成分。
选用聚酯多元醇是令人感到意外的，因为在现有技术中已知聚酯多元醇一般是具有低的耐水解性能。本发明指出了与现有技术相反的观点。
在制备已知聚氨酯的涂层中，反应混合物中NCO/OH之比为0.8时是特别有利的，与此相反，在本发明的一个优良方案中，使用具有NCO/OH当量比为0.9～1.1时，最好约为1的反应混合物时，这就是说按化学计量比计算。这样，在老化试验中获利了最好的性质。
按照本发明制备涂层，所用的反应混合物中可以含有添加剂，如铺展剂、有机溶剂、防光保护剂、防紫外线剂。这些添加剂一般都加到多元醇成分中。作为铺展剂，可以使用油和硅氧烷树脂（氧化烯基聚硅氧烷），以及氟代烷基酯。作为防光保护剂，可以使用其加入量为多元醇的0.5～2%（重量）的空间位阻的胺类。作为防紫外线剂，可以使用其加入量为多元醇的0.5～5%（重量）的取代苯并三唑。
按照本发明的涂层，一般是根据欧洲专利说明书0132198和0133090中所描述的那样通过浇铸反应混合物而形成的。
也可以用喷射反应混合物或反应注模法而形成。涂层可以在要涂覆的窗玻璃上就地形成。也可以在以后要移去的支承物上形成，而以后可任意将预先形成的涂层粘连到一层或更多层塑料层片上。所得层片以后可与基片一起装配成所要求的片材。
按照本发明的术语“涂层”包括在基片上的涂层以及含有一层或多层的单片。
按照本发明涂层的不同制备实施例描述如下：
例1
按重量计，460分1，6己二醇和70分三羟甲基丙烷与167分己二酸、56分邻-苯二甲酸和247分异-苯二甲酸进行酯化反应而得到一种含有4.3（重量）的游离OH基团而酸指数（德国工业标准（DLN）53.402）约为1的组合物。这样得到的轻度支链的聚酯多元醇组成了反应混合物的多元醇组分。在聚酯多元醇中加入0.1%（重量）的氟代烷基酯作为铺展剂和1%（重量）的双（1，2，2，6，6-五甲基-4-哌啶）癸二酸酯作为防光保护剂。
为制备反应混合物，取100克主要是三官能团的聚异氰酸酯、一种含有23%（重量）游离NCO基团的1，6-己二异氰酸酯的缩二脲与216克上述聚酯多元醇加热到80℃，并在该温度下搅拌10分钟。这样，反应混合物的NCO/OH的当量比是1。
两种成分混合后，将反应混合物在予先加热到70℃的玻璃平板上，用涂层刮刀铺成厚度为0.5毫米的涂层。涂好的玻璃板，例如在恒温控制的空气环流密闭器中，在90℃温度下保持30分钟，以硬化涂层。
这样制备的涂层硬化后，在相对湿度为50%、温度为20℃的条件下，将聚氨酯层由玻璃支承体上取下，以测定其机械性能和抗拉力，按照德国工业标准（DLN）53455测量其延伸的加长，并按德国工业标准53457测定其模数E。也按德国工业标准53515测量了对撕裂扩展的格雷夫斯（Graves）阻力。还按ECE标准R～43测量其耐磨性和用埃里克森（Eriehsen）方法测定了粘在玻璃支承体上的聚氨酯涂层的耐擦伤性。为用埃里克森方法测定其耐擦伤性，使用了在德国工业标准53799中所描述的实验设备，只是用以划痕的锥形金刚石的顶角为50度，锥顶的曲率半径为50微米。为计算耐擦伤性，记录了在涂层表面上看不到损伤时所加到划痕金刚石上的最大负载量。
聚氨酯涂层表面状态是用肉眼观察的。
机械测试的结果列于下面表1。表中也说明了，对不同机械性能聚氨酯涂层所处的测值范围，都能够满足在应用中所要求的标准，特别是其自复性能。
比较例
按例1的方法，但取81.3克的由1，2-环氧丙烷与含有约11.5%游离OH基团的2，2-双（羟甲基）-1-丁醇缩合而制得的分子量约为450的聚醚多元醇，并按多元醇的重量计，在多元醇中加入0.05%（重量）的二丁锡二月桂酸酯作为催化剂，0.1%（重量）的氟代烷基酯作为铺展剂，1%（重量）的1，2，2，6，6，-五甲基-4-哌啶作为防光保护剂。
表1说明了实例中的涂层的全部机械性能都在所要求极限值的范围之内。
为研究大气对表面的影响，取一定量的样品任意暴露在大气中，放置几个月时间。经过了这段时间，在聚氨酯表面上没有观察到状态的变化。亮度测量表明，有十分细小的，少于1%的亮度降低。
在比较例中，虽然使用了防光保护剂，但亮度降低超过了50%。
Figure 85109199_IMG1
例2
为制备反应混合物，将100克以含有游离NCO基团21.5%（重量）的1，6-己二异氰酸酯为基的异氰酸酯基团的主要是三官能团的聚异氰酸酯，与94.2克的含有9.3%（重量）的游离OH基团的三官能团的聚己酸内酯，在40℃时剧烈搅拌10分钟。这样，NCO/OH之比是1。作为聚己酸内酯的添加物，按聚己酸内酯的重量计，一开始就加入0.015%（重量）的二丁锡二月桂酸酯作为反应催化剂，0.1%（重量）的氟代烷基酯作铺展剂，和1%的双（1，2，2，6，6-五甲基-4-哌啶）癸二酸酯作防光保护剂。将这两组分混合后，将反应混合物在予先加热到70℃的玻璃平片上，用涂层刮刀铺成厚度为0.5微米的涂层。再在恒温控制的空气环流密闭器中，在90℃放置30分钟而使涂层硬化。
为检验不同环境条件对涂层老化的影响，将涂有这种聚氨酯层的玻璃板存放在不同的环境条件下，然后测定其机械和光学性能。下面表2列出了机械性能测试的结果，不同样品按照以下处理方法处置：
样品A：在聚氨酯层硬化后立即测量。
样品B：在正常环境条件的实验室中放置21天。
样品C：在空气环流密闭器中，在60℃的温度下放置2小时。
样品D：在50℃温度，100%相对湿度的大气中放置7天。
测量结果再一次表明，甚至经过变化很大的模拟老化处理后，物理-机械性能仍在所要求的极限范围之内，可以观察到在这些性质方面没有显著的变化。对另一些直接暴露在气候条件下的样品，是将涂有涂层的玻璃片在外面大气的直接作用下暴露几个月。暴露以后，用肉眼鉴定涂层并按德国工业标准67530方法测量其亮度。肉眼鉴
Figure 85109199_IMG2
定表明，在涂层的厚度内或表面上都没有明显的变化。亮度测量表明，与暴露在外面大气之前同一样品的测量值相比较，有十分轻度，约0.5%的表面亮度降低。
按照本发明的涂层可用于上面所说的全部使用中，也可以用于与具有吸能性质的聚氨酯层组合而形成如在欧洲专利说明书0132198和0133090中所描述的双层片料，这种双层片料宜用于叠层安全窗玻璃。

Claims (8)

1、一种用于窗玻璃或透明的玻璃物体和/或塑料的，具有自复性能的透明聚氨酯涂层，由含有一种多官能团的异氰酸酯成分和一种多官能团的多元醇成分所组成的反应混合物，和选用一种反应催化剂以及其他辅助物质所组成的，其特征在于，反应混合物的异氰酸酯成分是选自由含有15～25%(重量)NCO基团的1，6-己二异氰酸酯单体，如其缩二脲或其异氰酸酯所形成的主要为三官能团的脂族聚合物，而反应混合物的多元醇是选自含量3～12%(重量)OH基团的多官能团的聚酯多元醇。
2、根据权利要求1的聚氨酯涂层，其特征在于，用作多元醇成分的轻度支链的聚酯多元醇是基于含有3～5%（重量）OH基团的三羟甲基丙烷、1，6-己二醇、己二酸、邻-苯二甲酸和异-苯二甲酸。
3、根据权利要求1的聚氨酯涂层，其特征在于，将含有8～12%（重量）OH基团的三官能团的聚己酸内酯用作多元醇成分。
4、根据权利要求1～3之一的聚氨酯涂层，其特征在于，所用反应混合物的NCO/OH之比为0.9～1.1，最好是约1。
5、根据权利要求1～4之一的聚氨酯涂层，其特征在于，反应混合物至少含有以下一种添加剂：
二丁锡二月桂酸酯用作反应催化剂，0.05～0.15%（重量）的一种或多种化学化合物，如硅氧烷油、硅氧烷树脂或氟代烷基酯用作铺展剂，0.5～2%（重量）的双（1，2，2，6，6-五甲基-4-哌啶）癸二酸酯用作防光保护剂，选用0.5～5%（重量）的取代苯并三唑用作紫外线吸收剂。
6、含有一种根据权利要求1～5之一的涂层的窗玻璃。
7、一种塑料片料，其特征在于含有根据权利要求1～5之一的聚氨酯涂层。
8、根据权利要求7的片料，其特征在于，聚氨酯层是与具有吸能性质的聚氨酯层相组合的。
CN85109199A 1984-12-06 1985-12-06 一种用于窗玻璃，特别是受大气影响的窗玻璃的具有自覆性能的涂层 Expired CN1007989B (zh)

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